Copper-Catalyzed Enantioselective Decarboxylative Cyanation of Benzylic Acids Promoted by Hypervalent Iodine(III) Reagents.

Abstract

Copper-catalyzed asymmetric radical cyanation reactions have emerged as a powerful strategy for rapid construction of α-chiral nitriles. However, the directly decarboxylative cyanation reactions of common alkyl carboxylic acids remain largely elusive. Herein, we report a protocol for copper-catalyzed direct and enantioselective decarboxylative cyanation of benzylic acids. The in situ activation of acid substrates by a commercially inexpensive hypervalent iodine(III) reagent promoted the yield of the alkyl radicals under mild reaction conditions without prefunctionalization. The structurally diverse chiral alkyl nitriles were produced in good yields with high enantioselectivities. In addition, the chiral products can be readily converted to other useful chiral compounds via further transformations.